Higher alkanes (cyclohexane, n-pentane, n-heptane, methylbutane, 2-and 3methylpentanes, 3-methylhexane, cis-and trans-deealins) are oxidized at 20 °C by H202 in air in acetonitrile (or nitromethane) solution in the presence of the manganese(IV) salt L2Mn2032 (L = 1,4,7-trimethyl-1,4-7-triazacyclononane) as the catalyst. An obligatory component of the reaction mixture is acetic acid. Turnover numbers attain 3300 after 2 h, the yield of oxygenated products is 46% based on the alkane. The oxidation affords initially the corresponding alkyl hydroperoxide as the predominant product, however later these compounds decompose to produce the corresponding ketones and alcohols. Regio-and bond selectivities of the reaction are high: C(1) : C(2) : C(3) : C(4) --1 : 40 : 35 : 35 and 1 ° : 2 ° : 3 ° is 1 : (15--40) : (180-300). The reaction with both isomers of decalin gives (a~er treatment with PPh~) alcohols hydroxylated in the t~tiary positions with the cis/trans ratio of -2 in the case of cis-decalin, and of -30 in the case of trans-decalin (i.e. in the latter case the reaction is stereospecific). Light alkanes (methane, ethane, propane, normal butane and isobutane) can be also easily oxidized by the same reagent in acetonitrile solution, the conditions being very mild: low pressure (1-7 bar of the alkane) and low temperature (-22 to +27 °C). Catalyst turnover numbers attain 3100, the yield of oxygenated products is 22% based on the alkane. The yields of oxygenates are higher at low temperatures. The ratio of products formed (hydroperoxide : ketone : alcohol) depends very strongly on the conditions of the reaction and especially on the catalyst concentration (at higher catalyst concentration the ketone is predominantly produced).